Synthetic detergent bar



- cohesive solid mass.

SYNTHETIC DETERGENT BAR. j

Donald F. Searle, Napa, Calif., assignor' to California ResearchCorporation, San Francisco, Calif, a corporation of Delaware No Drawing.Application December 17, 1953 Serial N0. 398,892

9 Claims. c|. 252-138 The present invention relates. to'a sulfonatedetergent composition in the form of a solid bar or cake, which does notimpart an objectionably tacky feeling to the skin after washing and isnot susceptible to excessive and rapid erosion upon being wetted. t ,5

Considerable research endeavor has been, directed in the past toward theproduction of a satisfactory.allsynthetic sulfonate detergent bar orcakefor toilet and bath use. In the majority of sulfonatedetergentformulations the active detergent ingredient is analkylarylsulfonate i, e., a water-soluble salt of an alkyl aryl sulfonicacid, preferably a sodium salt. Sodium salts of C C monoalkyl arylsulfonic acids, and in particular sodium salts of C -C monoalkyl benzenesulfonic acids, are generally supplied to the trade because they do notform insoluble compounds with calcium and. magnesium .ions present inhard water. They aremanufactured by sulfonation of suitable alkylbenzene stocks, followed byneutralization of the sulfonation productmixture, and-- drying to the desired solid form. However, up to the.present day, the application of thesesulfonates in the manufacture ofall-synthetic or non-soap detergent-bars or cakes for toilet and bathuse has been greatly handicapped by the presence of a number ofundesirable characteristics. One of them is the occurrenceof anunpleasanttackysensation on the skin immediately after washing withthebar or cake containing the active sulfonate ingredient. The truereasons for the development. of this tackynsensation have not been sofar exactly determined-and are, infact, a subject of considerableconjecturing and debate; Nevertheless, the occurrence of this unpleasantfeeling is to a large extent responsible for the lag in consumeracceptance of alkyl aryl sulfonate all-synthetic detergent bars andcakes in competition with conventional soap bars and cakes. 1

Another serious drawback which contributes to the reluctance of theconsumers to accept these non-soap detergent bars or cakes isfound-inthetendency of -thesebars or cakes to undergo rapid erosion-whenleft n;the wet washstand, and, .particularly, when the water drainingoifthe detergent cake or bar after useremains in;;contact therewith owingto an incidental clogging of thedrain hole or strain-er in the dish orreceptacle. provided for thesoap. As a general rule, in formulatingsolid sulfonate detergent bars or cakes, at least 20% byweightofanorganic binder such as a starch or a vegetable gum is required to permitcompacting theingredients into. a firm philic colloidal compounds andon: contact with-water, even though it is present in comparatively smallamounts, absorb it rather rapidly, soften up, and the bar-b'reaks'up andcollapses as a smeary sludgein the soapidishn This annoying occurrenceof erosion issomewhat less pronounced when the detergent-formulation=iscompacted into an egg-shaped cake, as comparedzwithrectangular bars;nevertheless, it contributes markedly: toztheislushing and rapid run-outof the bar orflcake' at he These binder materials are hydro-.

surface of 2,845,391 "Patented July 29, 1958 contact with the soap-dishor washstand. In fact, it has been observed that the rate of erosion ofsulfonate detergent bars as a general rule is from 1 /2 to 2 timesfaster than thatof the conventional toilet soap.

Alkyl aryl sulfonate detergents, unless subjected to a special desaltingtreatment generally contain a substantial admixture of inorganic sulfateformed in the neutralization of the mixture of sulfonic acid andunreacted sulfuric acid, and a portion of this sulfate is present in thebody of the detergent bar or cake as decahydra'te. On drying after useand exposure to the atmosphere, dehydration ocv curs, and the bar orcake frosts, i. e., small crystals, or a coating of White dust of Na SOappear on the surface. The occurrence of this frosting is also objectedto by the user.

Various approaches toward elimination of the aforementioned drawbacks inthe preparation of all-synthetic sulfonate detergent bars and cakes fortoilet and bath use have been suggested in the past. For instance, ithas been proposed to introduce relatively large quantities of lecithinas 'a detackifier" into the formulation. However, the quantities oflecithin effective in exerting the desired detackifying action are from20 to 70% by weight of the total detergent formulation, and it isobvious that this technique introduces an unduly large amount of aningredient which has nothing to do with the detergent action and tendsto weaken it. In addition, the mixture containing so much lecithin, inthe presence of water (up to 15% by weight) required to facilitate thepreparation of satisfactory firm bars and cakes, tends to stick to themanufacturing equipment such as mills, plodders, etc. Furthermore, thepresence of lecithin in a sulfonate detergent bar or cake does notreduce the rate of erosion thereof by water after use.

Another suggestion aiming at the reduction of the rate of erosion ofsulfonate detergent bars and cakes involves introduction into the massof the detergent bar of certain fillers such as china clay or talc so asto provide a sufiiciently rigid, sponge-like network or skeleton of thefiller material which, upon erosion of the water-sensitive, sulfonatedetergent and starch binder from the moistened surface, would becomeexposed, decreasing the points of contact between the water-sensitiveingredients and the wet receptacle for the bar and, consequently, wouldtend to decrease dissolution of the bar.

1 This proposal, however, is far from being a satisfactory solution ofthe problem of manufacturing a sulfonate detergent bar for toilet use.First of all, the employment of china clay or talc in the largeproportions introduces an excess of extraneous inert material into thedetergent bar or cake. Secondly, the mixture of ingredients (active"sulfonate, detackifier such as lecithin, binder such as corn starch,etc.) containing clay or talc fillers is quite stiff and grainy, and tomaintain sufficient fluidity of the'mix- 'ture in the plodding, millingand molding equipment, it is necessary to increase considerably itslecithin content, introducing the drawback of stickiness to the parts ofthis equipment. Furthermore, the presence of an excess of filler such astalc weakens the cohesive strength of the final detergent bar or cakeand renders it susceptible to crumbling, besides causing an untowardincreasein'the density ofthe bar or cake product. The surface of theresulting shaped product is not glossy and, notwithstanding the verycareful selection of the finest grades of talc or clay, their presenceimparts a somewhatgritty feeling to the skin in the process of washing.

The present invention provides a new allesynthetic alkyl aryl sulfonatedetergent composition,'s'haped into bars, cakes or other forms suitablefor toilet and bath use, as well as for household laundering,dishwashing -and other washing applications where the use of solidshaped detergent is appropriate and would be preferred by the consumer.When exposed to contact with water drained off into the soap holder ofthe washstand, the solid, shaped sulfonate bar or cake displays amoderate rate of erosion comparable and often lower than that of thebetter popular toilet soaps; furthermore, no tacky sensation obtains onthe skin after these shaped solid compositions have been employed forwashing or bathing.

The only active detergent ingredient in such a shaped product is analkyl aryl sulfonate, preferably a sodium salt of C to C monoalkylbenzene sulfonic acid and desirably a sodium salt of C C monoalkylbenzene sulfonic acid. On account of the inherent stickiness of suchsulfonates, these ingredients should not 'bepre sent in the final shapedsolid product in anamount greater than 50% by weight thereof, and inbars or cakes for toilet or bath use preferably in proportions from 30to 40% by weight. When cakes or bars are to be used for launderingpurposes, dishwashing, and generally in applications where the so-calledheavy-duty laundry bar soaps containing substantial amounts of alkalinebuilders (such as tetrasodium pyrophosphate, sodium tripolyphosphates,

sodium carbonate, sodium meta-silicate, and the like) have heretoforebeen used, the alkyl aryl sulfonate ingredients are present in amountsranging from 15 to 30% by weight, and preferably from 20 to 25% byweight.

In addition to'the 'alkyl aryl sulfonate detergent in gredient the solidshaped composition of the invention contains a non-frosting sodium saltof an inorganic acid, this salt being moderately soluble (preferablyfrom about 2 to about in water at room temperature, and, furthermore,the composition contains a small amount of an alkaline earth metal saltor aluminum salt of a satu-' rated C -C fatty acid. The non-frostingsodium salts of inorganic acids being moderately soluble in water tendto saturate the water present in the soap-dish after only a small amounthas dissolved and thus prevent dissolution of the bar after beingwetted. They are present in the detergent bar or cake in an amountranging from 10 to 40% by weight thereof, preferably from to 35% byweight. Sodium bicarbonate and tetrasodium pyrophosphate areparticularly effective as anti-erosion ingredients of the solid; shapeddetergentcomposition of this invention, becausetheir solubility lieswithin the aforementioned range from 2 to 10%. On the other hand, sodiumsalts ofinorganic acids having a higher rate of solubility, e.g.,-disodium hydrogen phosphate, have been found to be ineffective forthe purpose of preventing rapid erosion, a bar containing 22% by weightof disodium hydrogen phosphate having collapsed completely in less than24- hours of soaking in water.

The alkaline earth metal salts and aluminum salts of saturated C -Cfatty acids-are added to prevent the occurrence of the unpleasant tackyfeeling on the skin after use. They are added in amounts which must beat least 1% of the total weight of the solid shaped composition, amOuntsranging from 1 to 2% by weight generally being satisfactory forall-practical purposes. The number of salts which can be so employedincludes, e. g., calcium stearate, aluminum stearate, magnesiumstearate, calcium myristate, aluminum palrnitate, calcium laurate andmagnesium laurate.-

Ordinarily, the formulation of anall-synthetic detergent bar or cakeprepared in accordance with'theinvention comprises an organic bindersuchasa starch or a vegetable gum. The presence of a binder, although notalways necessary, is usually preferred, because it facilitates mixing ofthe ingredients and subsequent milling, plodding and stamping of theproduct, by acting as a plasticizer; in addition, the binder exerts acohesive action in holding the ingredients together in the manufacturedbar. From 10 to 30% by weight of such a binder and even as high as 40%by weight may be pres ent in the composition. In most cases, however,.fIOm 10 to 25% of a starch such as corn starch, wheat starch,

potato starch, or the like, will adequately serve the manufacturingpurposes.

An important requirement for the production of an effective satisfactoryall-synthetic sulfon'ate detergent composition of the invention is a lowcontent of sodium sulfate admixture in the active sulfonate ingredient.This content should be lessthan about 5% by weight based on the totalweight of the solid shaped detergent composition.

The sulfonate detergent employed in formulating the composition of thepresent invention may be produced by any of the well-known methodsdescribed in the art, the techniques described in U. S. Patent No.2,477,383, issued to A. H. Lewis, being preferred.

When alkyl benzenes are sulfonated in accordance with the techniqueofthe aforementioned patent by means of strong sulfuric acid, e. g., 22%oleum, the resulting sulfonic acid mix is diluted with water to 80%sulfuric acid strength in order to obtain a more complete separation ofunreacted sulfuric acid from the sulfonic acid. The diluted mix is thenneutralized with aqueous caustic soda or'aqueous sodium carbonate and asulfonate product ,slurry having a sodium sulfonatezsodium sulfate ratioof 85:15 to 88:12 is obtained.

.weight of moisture is fed into a plodder.

with the invention. Among these substances are included:

fillers such as china clay and talc; plasticizers such as alkylolamines, e; g., triethanolamine, and water-soluble waxes, e. g., thoseknown in the trade under the common name of Carbowax"; pigments (e. g.,titania and zinc oxide) and other coloring agents; antiseptics;perfumes; extenders (e.'g., carboxymethyl cellulose), etc. If desired,these solid shaped compositions may also include effective amounts ofN-alkyl glycine additives, such as are described by R. D. Stayner in hisU. S. patent application Serial No. 343,257, as capable of preventingskin rashes and erythemas in persons allergic to sulfonates. Glycerinemay also be added to improve lathering property and to impart thefeeling of slipperiness characteristic of the better soaps. Except forthe fillers such as talc and china clay which may be present in amountsup to 20% by weight of the total formulation, all other optionalingredients are employed in small amounts conventional in the soapmanufacture, i. e., they are seldom present in the formulations inamounts exceeding 10% by weight thereof, and generally are present inamounts less than 5% by weight. The solid shaped compositions of theinvention also contain a certain percentage of moisture, the presence ofwhich facilitates the plodding and milling, and aids the plasticity ofthe bar or cake. This moisture or water content, as a rule, is lowerthan 15% by weight of the total formulation in bars intended for toiletand bath use, and not higher than 20% by weight in heavy-duty bars to beused in laundering and dishwashing.

The preparation of solid shaped all-synthetic sulfonate detergentcompositions of the present invention follows the general lines of theconventional practice of manufacturing milled toilet soaps. The severalsolid and liquid ingredients are mixed together in an amalgamator, andthe resulting loose mixture containing less than 15% by After passingthe mixture several times through the plodder (or a series of plodders),the extruded material which emerges from the plodder in the form of acontinuous cylinder about 1 inches in diameter is cut into lengths andthese are stamped in a mold. .If a finer product of a texture resemblingthat of the better milled toilet soaps is desired, the mixture ofingredients leaving the amalgamator is introduced into the plodder, andthen is fed into the plodding and stamping equipment. The wholeoperation can be effected at room temperature. If difliculties develop,owing to the materials sticking to the mold, it may be dusted withtalcum, or mold-release fluids, e. g., glycerine-brine, may be employedin conventional manner. 7 A number of examples are offered hereinafterto indicate the problems involved in the preparation and application ofall-synthetic sulfonate detergent cakes and bars for toilet use and toshow that these problems are decreased and eliminated by thepreparationof the shaped solid detergent products of the present invention. Inthese examples the amounts are given in percent by weight. The sulfonatedetergent employed is sodium C -C polypropylene benzenesulfonateprepared in accordance with the aforementioned U. S. Patent No.2,477,383, issued to A. H. Lewis. The starch binder, whenever employed,is corn starch. In some of the examples watersoluble high molecular wax'is present as a plasticizer; this wax is a polyglycol product of amolecular weight of about 1,540, manufactured by the Carbide & CarbonChemicals Division of New York, New York, under the trade-name Carbowax1540. The amount of moisture present in the various mixtures ofingredients were as high as%, amounts from 6 to 8% having been found tofurnish the optimum results insofar as the efliciency of manufacturingand the quality of the final bar or cake is concerned. The solid shapedproducts prepared in the laboratory in accordance with the generalprocedure outlined hereinabove and described in the examples .had thefollowingdimensions: length, 2%; width, 2%; thickness, about 1".

The rate of erosion was determined by placing the finished bar or cakeinto a beakercontaining 200 cc. of

cold distilled water and letting it soak at room temperature for twodays, whereupon the fluidized matter was sloughed olf, and thepercentage (rate) of erosion determined by weighing the undissolvedremainder ofthe bar or cake and computing the ratio of the liquefied materialto the original weight of the bar.

Q The frosting tendency wasestimated'visually by per- ;mitting thetoilet barto dry. after use and observing its surface after 24hours.Frosting was rated as heavy,

oil vsoap.

The following four examples illustrate the increase of objectionablefrosting with an increasing content of soduim sulfate in the bar, facedin;the past by the formulators of sulfonate detergent bars:

Example 1 Since this bar does not contain sodium sulfate, no frostingcould be observed, althoug h thesensation of stickiness on the skinafter washing was quite pronounced and thus rated as heavy. Thebar wassoft andivor y in color.

visually with the lathering power and detergency of .three :differentbars of good-qualityamixed' tallow and coconut 1 :Thebar in this examplewas substantiallyifree of sodium ulate andhad the followingcomposition:

-; V, Percent Active sulfonate, 50 gCorn starch 20 Talc 20 Carbowax Q. 2-Water 7 Zinc oxide 1 No frosting was observed 24 hours after beingused, but a moderate degree of-stickiness was felt on the hands afteruse.

Example 3 V This bar h d higher, content of sodium sulfate than the onein Example 2, being of the following composition:

I Percent Active sulfonate 45 Sodium sulfate 5 Corn starch 20 Talc 20Carbowax -I 2 Water 7 Zinc oxide 2 1 A slight degree of frosting wasobserved 24 hours after being used; the sensation of stickiness on thehands was of about the same order as in Example 2.

"Example 4 This bar had an even greatercontentof sodium sulfate than thebars in' the two preceding examples. Its sulfonate content was 40% andits sodium sulfate content was 1 0%, the amounts of other ingredientswere the sameas in Examples 2 and 3. Frosting observed 24 hours afteruse was heavy, while the feeling'of stickiness was of the same order asinExamples 2, and 3. The barsin each of Examples 2,?! and '4 were ofafirm texture and white in color. The surface, glossy'upon preparation,became dull after use;

The nextsix examples areofferedto show the effect of various additiveson :the occurrence of the sensation of stickinesson the skin afterwashing: of triethanolamine, in Example 8;v of lecithin, in Example 9;and, particularly, of alkalineearth metal salts and aluminum salts ofsaturated C1 4.c20 fatty acids, in Examples 5, 6 and 7. Example 10isgiven to show that the employment of a starch -binde r is optional, andthat starch may be omitted, the active sulfonate itself providing asuflicient degree of cohesiveness Example 11 is given to show that thepresence of an inert filler(ta1c)is likewise not critical for thepreparation of a flrmbar.

Calcium stearate V i The bar frosted heavily 24 hours after beingused,but the feeling of stickiness was'very slight. This bar had a firmtexture and was'ivo'ry' in color; The originally glossy surface becamesomewhat jdull'a'ft'er use"; I

Example6 This bar was of a practically identical composition as that ofExample 5, except that calcium stearate was replaced by an'equivalentamount of aluminum stearate. Frosting'was noted to be heavy, butstickiness after use was very slight. The bar was firm, quite glossy atfirst, and ivory in color."

Example 7' This bar had the same composition as that of Example 5,except for the content of calcium stearate which was increased to 2% byweight at the expense of the moisture contentreduced to 6%. Frostingcontinued to be heavy, but the feeling of stickiness was exceedinglyslight. The original texture of the bar remained firm. Its color waslight ivory.

Example 8 The composition of this bar was as follows:

Percent Active sulfonate 30 Sodium sulfate 20 Corn starch 20 Talc 20Carbowax 2 Water 4 Triethanolamine 4 Frosting was moderate, possibly asa result of the presence of triethanolamine plasticizer, but thesensation of stickiness after use was much more pronounced than inExamples 5, 6 and 7, and was rated as moderate. In addition, the bar,even though possessing a satisfactory ivory color, had too soft atexture.

This bar, after having been used and leftto dry for 24 hours, frostedheavily and produced a moderate sensation of stickiness on the handsafter washing.

Addition of lanolin, olive oil, stearic acid, sodium benzoate and'caseinin amounts which ranged from 2 to 10% by weightof the total composition,in lieu of lecithin of Example 9 above, were found to be likewiseineffective for the purpose of reducing the sensation of stickiness onthe handsafter use. V

Example 10 The bar had the following composition:

V Percent Active sulfonate 44.0 Sodium sulfate 29 Talc 20 Carbowax 2Water Frosting observed 24,hours after use was heavy, and a moderatedegree of stickiness was felt on the hands after washing.

Example I] The bar had the following compositiont a 1 Percent Activesulfonate .48 Corn starch. v 40 Water 7 .10" Calcium stearate 2 Nofrosting appcared24 hours after use, and the feeling of stickiness afterwashing the hands was very slight. When tested for 48 hours for erosiontendency, the bar was found to be 79.6% by weight eroded. The absence oftalcum in this composition seemsto have no adverse effect on theformation of a firm bar having a smooth, glossy surface and ivory incolor. j

Examples 13, 14 and 15 bring forward the several advantageous featuresof the solid shaped detergent compositions of the present inventionobtained by bringing together the essential ingredients thereof in theproportions hereinbefore specified, as compared with Example 12 of anall-synthetic sulfonate bar which did not contain the ameliorativeingredients and with 1Example l6 It frosted heavily 24 hours after useand imparted a moderate feeling of stickiness to the hands upon washing.When tested 48 hours for erosion tendency, it was found to be eroded,although when manufactured this bar was firm and possessed asatisfactory glossy surface of a darker shade of ivory color.

Example 13 The composition of this bar was as follows:

Percent Active sulfonate 39.7 Sodium sulfate 5.9 Sodium bicarbonate 22.7Corn starch 22.7 Water 9 The presence of sodium bicarbonate in theamount within the operative range from 10 to 40% by weight of the totalcomposition reduced erosion to 34.7%. A slight degree of frostingappeared 24 hours after use, owingto the sodium sulfate content beingslightly higher than the permissible maximum. The bar lathered well ineither soft (50 p. p. m. of combined Mg-Ca hardness) or hard water (200p. p. m. of Mg-Ca hardness) and had a good washing action.

Example 14 The bar in this example had the following composition:

V Percent Active sulfonate 31.5 Sodium sulfate 4.7 Sodium bicarbonate16.5 Corn starch 40 .Water 6.3

Aluminum stearate 1 This composition included sodium bicarbonate as theerosion-reducing additive and aluminum stearate as the stickinessinhibitor. After washing the hands with the bar, practically no sticky'sensation was felt on the skin. Frosting was substantially absent. Theresults of the 48-hour determination of erosion tendency gave a rate oferosion of a mere 32.7%. The surface of the barwas glossy, its texturewas firm, and the color was light yellow.

Detergency and lather-ing werecomparable to those of good-quality soaps.

Example 15 Percent Active sulfonate 30.8 Sodium sulfate 4.6 Tetrasodiumpyrophosphate 36.8 Corn starch 20.6

Water 6.2 Calcium stearate 1 Frosting was substantially absent. Thestickiness sensation after washing was practically absent, and the 48-hour determination of the erosion tendency gave a value of a mere 37.1%.The barhad a firm texture with a rather dull surface and was light brownin color. Detergency and lathering were comparable to those ofgoodquality soaps.

Example 16.Cntral test with three diflerent soaps Example 17 The bartested in this example had the following composition:

Percent Active sulfonate 25 Sodium sulfate 3.5 Tetrasodium pyrophosphate25 Corn starch 25 Sodium carboxymethyl cellulose 1.2 Water 19.3 Calciumstearate 1.0

The bar was light brown in color and had a rather soft texture owing tothe high content of moisture. After being used and left to dry for 24hours, this laundry-type sulfonate detergent bar showed about the samerate of erosion as the sulfonate toilet bar of Example 15. The sensationof stickiness after use on the skin was slight. Detergency and latheringwere of the same order as those of conventional-cast laundry soap bars.

Example 18 In this example, a laundry type all-synthetic detergent bar,milled in the same manner as described herein above, had the followingcomposition:

Percent Active sulfonate ..20 Sodium sulfate 3.0 Tetrasodiumpyrophosphate 30.5 Corn starch 30.5

Calcium stearate 1.0 Water 15.0

This bar was likewise light brown in color, but had a firmer textureupon being used and left in the soap-dish for 24 hours; it showed a rateof erosion of the order of 35%. Stickiness sensation on the skin afteruse was practically nil. Detergency and lathering were of the same orderas in the preceding example.

The aforegiven examplesestablish beyond doubt the advantagesof theall-synthetic sulfonate deter gent solid "s h'aped compositions of thepresent invention. The practical absence of the sensation of stickinesson the hands after use, and the low rate of erosion, e'quivalentto andoften lower than that of the better brands of toilet soaps, make theseuseful all-syntheticproducts attractive to the consumers in competitionwith conventional-milled toilet soaps and cast-laundry soap bars.

This application is a continuationin-part of my 00* pending applicationSer. No. 383,403, filed in the United States Patent Office on September30, 1953, and now abandoned.

It is to be understood thatapplicant does not limit himself to thespecific examples, given hereinabove merely to illustrate his invention,except as set forth in the following claims.

I claim:

1. A solid shaped synthetic detergent composition which comprises as itsessential components: (1) a sodium C C monoalkyl benzene sulfonate; (2)a nonfrosting sodium salt of an inorganic acid selected from the groupconsisting of sodium bicarbonate and tetrasodium pyrophosphate; (3) asalt selected from the group consisting of alkaline earth metal andaluminum salts of saturated C14C20 fatty acids; (4) a starch binder; (5)sodium sulfate in an amount ranging from 0 to less than 5% of the totalweight of said five components, the proportions by weight of saidcomponents (1), (2), (3) and (4) on the basis of the total weight ofparts of said five components lying within the following ranges:

Component: Parts 1. Sulfonate 30 to 50 2. Non-frosting salt of inorganicacid 10 to 40 3. Salt of saturated fatty acid 1 to 2 4. Starch 10 to 40said composition containing not more than 20 parts of water per 100parts of the total weight of said five components.

2. A solid shaped synthetic detergent composition for toilet and bathuse consisting essentially, in parts by weight, of (1) to make 100parts: 15 to 50 parts of sodium C -C monoalkyl benzene sulfonate, 0 to 5parts sodium sulfate, 10 to 40 parts of an inorganic salt selected fromthe group consisting of sodium bicarbonate and tetrasodiumpyrophosphate, 1 to 2 parts of a salt of a saturated C -C fatty acid anda metal selected from the group consisting of aluminum and alkalineearth metals; and (2) about 6 to 20 parts water.

3. Composition according to claim 2 wherein the alkaline earth metal ofthe saturated fatty acid salt is calcium stearate.

4. Composition according to claim 2, wherein the sodium C C monoalkylbenzene sulfonate is present in an amount of 20 to 30 parts.

5. Composition according to claim 2 wherein the sodium C C monoalkylbenzene sulfonate is present in an amount about 30 to 50 parts.

6. Composition according to claim 5 wherein the sodium monoalkyl benzenesulfonate is a sodium C -C monoalkyl benzene sulfonate. I

7. Composition according to claim 5 wherein the inorganic salt selectedfrom the group consisting of sodium bicarbonate and tetrasodiumpyrophosphate is present in an amount of 15 to 35 parts.

8. Composition according to claim 7 wherein the monoalkyl benzenesulfonate is present in an amount of 30 to 40 parts.

9. A solid shaped synthetic detergent composition for toilet and bathuse consisting essentially, in parts by weight, of (1) to make 100parts: 30 to 50 parts of sodium C C monoalkyl benzene sulfonate, 0 to 5parts of sodium sulfate, 15 to 35 parts of an inorganic salt selectedfrom the group consisting of sodium bicarbonate and tetrasodiumpyrophosphate, 1 to 2 parts of a salt of a saturated C -C fatty acid anda metal se- 5 lected from the group consisting of aluminum and alkalineearth metals, 10 to 30 parts of a starch binder; and

(2) about 6 to 20 parts of water.

References Cited in the file of this patent UNITED STATES PATENTS HoytMar. 23, 'Malkemus Feb. 22, Walters June 23, Turck May 18, Lewis Feb.14,

1. SULFONATE ---------------------------------- 30 TO 50
 1. A SOLIDSHAPED SYNTHETIC DETERGENT COMPOSITION WHICH COMPRISES AS ITS ESSENTIALCOMPONENTS: (1) A SODIUM C12-C15 MONOALKYL BENZENE SULFONATE; (2) ANONFROSTING SODIUM SALT OF AN INORGANIC ACID SELECTED FROM THE GROUPCONSISTING OF SODIUM BICARBONATE AND TETRASODIUM PYROPHOSPHATE; (3) ASALT SELECTED FROM THE GROUP CONSISTING OF ALKALINE EARTH METAL ANDALUMINUM SALTS OF SATURATED C14-C20 FATTY ACIDS; (4) A STARCH BINDER;(5) SODIUM SULFATE IN AN AMOUNT RANGING FROM 0 TO LESS THAN 5% OF THETOTAL WEIGHT OF SAID FIVE COMPONENTS, THE PROPORTIONS BY WEIGHT OF SAIDCOMPONENTS (1), (2), (3) AND (4) ON THE BASIS OF THE TOTAL WEIGHT OF 100PARTS OF SAID FIVE COMPONENTS LYING WITHIN THE FOLLOWING RANGES: 2.NON-FROSTING SALT OF INORGANIC ACID -------- 10 TO 40
 3. SALT OFSATURATED FATTY ACID --------------- 1 TO 2
 4. STARCH------------------------------------- 10 TO 40